MIL-53(Al)-MOF sorbents in dispersive micro-solid phase extraction of penicillins from water

Abstract

Penicillin is an antibiotic that presents serious environmental risks because of its extensive use and ends up in our water bodies. This work presents the development and application of a dispersive micro-solid phase extraction (D-µ-SPE) procedure utilising the metal-organic framework MIL-53(Al) as a suitable adsorbent for preconcentration of piperacillin (PIP) and penicillin V (PNV) from water. The prepared MIL-53(Al)-MOF was characterised using various characterisation techniques. Following the extraction and preconcentration processes, a high-performance liquid chromatography-diode array detector (HPLC-DAD) was employed to separate and quantify PIP and PNV. The fractional factorial design (FrFD) and Box-Behnken design (BBD) were utilised to investigate parameters influencing the d-μ-SPE method for PIP and PNV. The maximum percentage recoveries were obtained under the following conditions: 5.5, 50 mg, 17.5 min, 1000 µL, and 10 min for pH, mass of adsorbent extraction time, eluent volume, and desorption time, respectively. High adsorption capacities for PIP (175 mg/g) and (217 mg/g) were achieved. The highest adsorption affinity toward zwitterionic analytes and quick kinetics of the adsorbent made the d-μ-SPE effective in extracting target analytes from various water matrices. The remarkable performance was attributed to electrostatic, hydrogen bonding, π–π and hydrophobic interactions. The pseudo-send order kinetics and Langmuir models described the adsorption data well. Under optimum conditions, the relatively low detection limits of 0.10–0.18 µg/L and wide linear range of 0.3–800 µg/L validated the effectiveness of the developed d-μ-SPE method. Applying the established d-µ-SPE/HPLC-DAD method to real water analysis verified its applicability and feasibility. In wastewater samples, PIP and PNV were found in the ranges of 0.71–1.12 µg/L for influent and 0.32–0.45 µg/L for effluent. PIP and PNV spike recoveries ranged from 91.7 % to 99.1 % and 93.2 % to 98.1 %, respectively, while the method's intraday and interday precision was <5 %. This work illustrates that the d-μ-SPE, in tandem with MIL-53(Al)-MOF, offers several advantages, including simplicity, rapidity and low solvent consumption for the recovery of penicillin from contaminated water sources.

HIGHLIGHTS • MIL-53(Al)-MOF with attractive functional groups was successfully synthesized following a solvothermal techniques. • The prepared MIL-53(Al)-MOF has large adsorption capacities for piperacillin (175 mg/g) and penicillin V (217 mg/g). • The MIL-53(Al)-MOF/D-μ-SPE of piperacillin and penicillin V achieved high % recoveries with a range of 91–99 from environmental water and wastewater.